Citation: Meng-Hao Li, Hui Hui, Yan Wang, Weiwei Huan, Ying-Wei Yang. Engineering macrocyclic nanoconfinement in covalent networks via internal charge redistribution for defined photocatalysis and adsorption[J]. Chinese Chemical Letters, ;2026, 37(8): 112016. doi: 10.1016/j.cclet.2025.112016 shu

Engineering macrocyclic nanoconfinement in covalent networks via internal charge redistribution for defined photocatalysis and adsorption

Meng-Hao Li ^{a, 1} ,
Hui Hui ^{a, 1} ,
Yan Wang ^{a, *,} ,
Weiwei Huan ^{b, *,} ,
Ying-Wei Yang ^{a, *,}

a.
International Joint Research Laboratory of Nano-Micro Architecture Chemistry, College of Chemistry, Jilin University, Changchun 130012, China
b.
Zhejiang Provincial Key Laboratory of Chemical Utilization of Forestry Biomass, College of Chemistry and Materials Engineering, Zhejiang A&F University, Hangzhou 311300, China

wangy2011@jlu.edu.cn

huanweiwei@zafu.edu.cn

ywyang@jlu.edu.cn

Received Date: 15 August 2025
Revised Date: 13 October 2025
Accepted Date: 22 October 2025
Available Online: 24 October 2025

Figures(5)

Mimicking natural energy conversion processes, the pursuit of metal-free porous organic polymers (POPs) as heterogeneous catalysts for photocatalytic oxidation is a major driving force in materials science, seeking to achieve high-performance artificial photochemical systems. In this work, we report the bottom-up synthesis of a hydrazone-linked pillararene POP in its keto form. The inherent pillararene cavities provide a unique nanoconfinement environment, enabling effective substrate recognition and electron enrichment, thereby facilitating sensitive photo-response and efficient photoenergy-to-chemical energy conversion for photocatalytic oxidation coupling of primary amines (up to 99% conversion). Crucially, the framework’s tautomeric state is precisely modulated via an irreversible keto-to-enol conversion using sodium borohydride reduction. This controlled tautomerism permanently tunes the nanoconfinement microenvironment, amplifying the polymer’s electron-rich character and optimizing pore electrostatic properties. Leveraging this tunable nanoconfinement, the resulting enol form framework achieves highly efficient adsorption of cationic pollutants (up to 95% removal for Rhodamine B). This work establishes tautomerism as a chemical tool to engineer nanoconfinement in macrocycle-based POPs, expanding the toolbox for advanced porous materials with tailored functionalities for diverse applications like photocatalysis and adsorption.
- Supramolecular chemistry,
- Pillararenes,
- Porous materials,
- Photocatalysis,
- Porous organic polymers
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